WO2010087394A1 - Alcohol compound having dioxane structure and process for producing same - Google Patents

Alcohol compound having dioxane structure and process for producing same Download PDF

Info

Publication number
WO2010087394A1
WO2010087394A1 PCT/JP2010/051110 JP2010051110W WO2010087394A1 WO 2010087394 A1 WO2010087394 A1 WO 2010087394A1 JP 2010051110 W JP2010051110 W JP 2010051110W WO 2010087394 A1 WO2010087394 A1 WO 2010087394A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
alcohol compound
integer
general formula
benzene
Prior art date
Application number
PCT/JP2010/051110
Other languages
French (fr)
Japanese (ja)
Inventor
小黒　大
Original Assignee
三菱瓦斯化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三菱瓦斯化学株式会社 filed Critical 三菱瓦斯化学株式会社
Priority to US13/146,752 priority Critical patent/US8324407B2/en
Priority to JP2010548547A priority patent/JPWO2010087394A1/en
Priority to CN201080006099.6A priority patent/CN102300856A/en
Priority to EP10735859A priority patent/EP2392569A4/en
Publication of WO2010087394A1 publication Critical patent/WO2010087394A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
    • C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/335—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
    • A61K31/357—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having two or more oxygen atoms in the same ring, e.g. crown ethers, guanadrel
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds

Definitions

  • the present invention relates to an alcohol compound having a dioxane structure and a method for producing the same, and more particularly, a cyclic alcohol compound useful as a raw material and an intermediate such as a paint, an adhesive, a pharmaceutical, cosmetics, food additive and surfactant It relates to a method of producing a compound.
  • Alcohol compounds having a dioxane structure are known as intermediates of cyclic acrylic acid esters which are raw materials for paints, adhesives and the like.
  • Patent Document 1 discloses a cyclic alcohol compound obtained by the reaction of benzaldehyde and trimethylolpropane as an intermediate of a cyclic acrylic acid ester.
  • the cyclic alcohol compound obtained by the reaction of benzaldehyde and trimethylolpropane described in Patent Document 1 may have limited applications in terms of solubility, reactivity, heat resistance, and the like.
  • An object of the present invention is to provide cyclic alcohol compounds useful as raw materials and intermediates for paints, adhesives, pharmaceuticals, cosmetics, food additives and surfactants, and to provide methods for producing the compounds.
  • the present invention provides an alcohol compound represented by the following general formula (1).
  • A represents an aromatic ring selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene and pyrene
  • R 1 is an alkyl group having 1 to 12 carbon atoms, substituted or unsubstituted 6 to 10 carbon atoms
  • n represents an integer of 0 to 4, provided that when A is benzene, n represents an integer of 1 to 4.
  • plural R 1 s may be the same as or different from each other R 2 represents a hydrogen atom, a methyl group or an ethyl group)
  • the alcohol compounds of the present invention can be suitably used as raw materials and intermediates for paints, adhesives, pharmaceuticals, cosmetics, food additives, surfactants and the like.
  • various kinds of pharmaceuticals, cosmetics, food additives, surfactants and the like can be produced by using the alcohol compound of the present invention as a raw material or an intermediate.
  • the alcohol compound of the present invention is a compound represented by the following general formula (1).
  • A represents an aromatic ring selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene and pyrene.
  • R 1 represents an alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a halogen atom.
  • the alkyl group in the present invention is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, preferably 1 to 9 carbon atoms, more preferably 1 to 4 carbon atoms, and specific examples thereof include a methyl group and an ethyl group.
  • the aryl group in the present invention is a substituted or unsubstituted aryl group having 6 to 10, preferably 6 to 8 carbon atoms, and specific examples thereof include a phenyl group, an iodophenyl group, a hydroxylphenyl group, a dihydroxyphenyl group, and methoxyhydroxy A phenyl group, ethoxy hydroxyphenyl group etc. are mentioned.
  • R 1 is particularly preferably an isopropyl group or a phenyl group.
  • n represents an integer of 0 to 4. However, n is an integer of 1 to 4 when A is benzene. When n represents an integer of 2 to 4, the plurality of R 1 s may be the same as or different from each other, but are more preferably the same. n is preferably 0 or 1 from the viewpoint of the availability of the raw material.
  • R 2 represents a hydrogen atom, a methyl group or an ethyl group.
  • the alcohol compound represented by the general formula (1) is preferably an alcohol compound represented by any one of the following general formulas (2) to (4).
  • R 2 has the same meaning as R 2 in the general formula (1), and the preferred range is also the same.
  • Preferred specific examples of the alcohol compound represented by the above general formula (1) include 2- (biphenyl-4-yl) -5-ethyl-5-hydroxymethyl-1,3-dioxane, 2- (biphenyl-4) -Yl) -5-methyl-5-hydroxymethyl-1,3-dioxane, 2- (biphenyl-4-yl) -5-hydroxymethyl-1,3-dioxane, 2- (isopropylphenyl-4-yl) -5-ethyl-5-hydroxymethyl-1,3-dioxane, 2- (1-naphthyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane etc., but the present invention is not limited thereto. I will not.
  • the manufacturing method of the alcohol compound represented by said General formula (1) is not specifically limited, To 1 mol of aromatic aldehydes represented by the following general formula (A), trimethylol methane, trimethylol ethane, or trimethylol propane is mentioned. And the like are preferably produced by reacting 1 to 5 moles, preferably 1 to 2 moles, more preferably 1 to 1.2 moles of a trihydric alcohol such as By using a trihydric alcohol in the above range, the formation of by-products can be significantly reduced and the production efficiency is improved.
  • a trihydric alcohol in the above range, the formation of by-products can be significantly reduced and the production efficiency is improved.
  • the reaction temperature is preferably 20 to 200 ° C., more preferably 100 to 180 ° C., particularly preferably 120 to 160 ° C.
  • the above-mentioned aromatic aldehyde be dropped in an organic solvent solution of a trihydric alcohol under acid catalyst to be reacted. This can significantly reduce the formation of by-products and can improve the production efficiency. During the reaction, it is preferable to distill off water in the solvent by means of a Dean-Stark tube or the like.
  • an acid catalyst such as hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid and the like, and p-toluenesulfonic acid is particularly preferable.
  • the amount of acid catalyst used is preferably 0.1 to 30% by mass, particularly preferably 1 to 20% by mass, with respect to the aromatic aldehyde.
  • the reaction solvent used in the present invention is not limited, but aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, anisole; amide solvents such as dimethylformamide, dimethylacetamide; ethers such as tetrahydrofuran, dioxane, dioxolane And ester solvents such as ethyl acetate and butyl acetate.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, anisole
  • amide solvents such as dimethylformamide, dimethylacetamide
  • ethers such as tetrahydrofuran, dioxane, dioxolane
  • ester solvents such as ethyl acetate and butyl acetate.
  • toluene, dimethylformamide and dimethylacetamide are preferred.
  • Example 1 [Synthesis of 2- (biphenyl-4-yl) -5-ethyl-5-hydroxymethyl-1,3-dioxane] 2000 ml of dimethyl acetamide (hereinafter referred to as DMAc, special grade: Wako Pure Chemical Industries, Ltd., special grade), 700 ml of toluene (special grade, Wako Pure Chemical Industries, Ltd.), trimethylolpropane (Wako Pure Chemical Industries, Ltd. 8 g (0.74 mol) made of special grade) and 20 g of p-toluenesulfonic acid dihydrate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) were added and stirred at 100 ° C.
  • DMAc dimethyl acetamide
  • TMS tetramethylsilane
  • the chemical shift value of 1 H-NMR in a solvent of heavy dimethyl sulfoxide (hereinafter referred to as heavy DMSO, manufactured by Wako Pure Chemical Industries, Ltd., special grade) of the obtained product is 0.1. 8-0.9 (t, 3 H), 1.6-1.7 (q, 2 H), 3.4 (s, 2 H), 3.6-3.8 (dd, 4 H), 4.7 ( s, 1 H), 5.5 (s, 1 H), 7.3-7.8 (m, 9 H).
  • Example 2 Synthesis of 2- (biphenyl-4-yl) -5-methyl-5-hydroxymethyl-1,3-dioxane
  • the synthesis and analysis were carried out in the same manner as in Example 1 except that trimethylolpropane was changed to trimethylolethane.
  • the yield was 91%.
  • the chemical shifts of 1 H-NMR in a heavy DMSO solvent of the product obtained are 1.0 (s, 3 H), 3.4-3.9 (m, 6 H), It was 4.7 (s, 1 H), 5.9 (s, 1 H), 7.4-7.5 (m, 9 H).
  • Example 3 [Synthesis of 2- (biphenyl-4-yl) -5-hydroxymethyl-1,3-dioxane] The synthesis and analysis were carried out in the same manner as in Example 1 except that trimethylolpropane was changed to trimethylolmethane. The yield was 89%.
  • the chemical shifts of 1 H-NMR in a heavy DMSO solvent of the product obtained are 1.8 (s, 1 H), 3.4-3.9 (m, 6 H), It was 4.7 (s, 1 H), 5.9 (s, 1 H), 7.4-7.5 (m, 9 H).
  • Example 4 Synthesis of 2- (isopropylphenyl-4-yl) -5-ethyl-5-hydroxymethyl-1,3-dioxane
  • the synthesis and analysis were carried out in the same manner as in Example 1 except that 4-biphenylaldehyde was changed to cuminaldehyde.
  • the yield was 92%.
  • the chemical shifts of 1 H-NMR in a heavy DMSO solvent of the obtained product ( ⁇ ppm, based on TMS) are 0.9 (t, 3 H), 1.2 (d, 6 H), 1.7 (1.7 ppm). q, 2H), 2.9 (m, 1 H), 3.4-3.9 (m, 6 H), 4.7 (s, 1 H), 5.9 (s, 1 H), 7.2-7 .4 (dd, 4H).
  • Example 5 Synthesis of 2- (1-Naphthyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane
  • the synthesis and analysis were carried out in the same manner as in Example 1 except that biphenylaldehyde was changed to naphthylaldehyde.
  • the yield was 87%.
  • the chemical shifts of 1 H-NMR in a heavy DMSO solvent of the obtained product ( ⁇ ppm, based on TMS) are 0.8-0.9 (t, 3 H), 1.6-1.7 (q) , 2H), 3.4-3.8 (m, 6H), 4.7 (q, 1H), 5.5 (s, 1H), and 7.0-8.2 (m, 7H). .
  • the alcohol compounds of the present invention can be suitably used as raw materials and intermediates for paints, adhesives, pharmaceuticals, cosmetics, food additives, surfactants and the like, and have high industrial value.
  • the alcohol compound of the present invention can be used as a raw material or an intermediate, and various paints, adhesives, pharmaceuticals, cosmetics, food additives are added. Substances and surfactants can be produced, and the technology can be enriched.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Birds (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
  • Cosmetics (AREA)

Abstract

An alcohol compound useful as a starting material or intermediate for coating materials, adhesives, medicines, cosmetics, food additives, surfactants, etc., and a process for producing the compound. The alcohol compound is represented by general formula (1) (wherein A represents an aromatic ring selected from a group consisting of benzene, naphthalene, anthracene, phenanthrene, and pyrene rings; R1 represents a C1-12 alkyl, an (un)substituted C6-10 aryl, or a halogen atom; n is an integer of 0-4, provided that when A is a benzene ring, n is an integer of 1-4 and that when n is an integer of 2-4, the multiple R1s may be the same or different; and R2 represents a hydrogen atom, methyl, or ethyl).

Description

ジオキサン構造を有するアルコール化合物及びその製造方法Alcohol compound having dioxane structure and method for producing the same
　本発明は、ジオキサン構造を有するアルコール化合物及びその製造方法に関し、詳しくは、塗料、接着剤、医薬品、化粧品、食品添加物及び界面活性剤等の原料及び中間体として有用な環状アルコール化合物、並びに当該化合物を製造する方法に関する。 The present invention relates to an alcohol compound having a dioxane structure and a method for producing the same, and more particularly, a cyclic alcohol compound useful as a raw material and an intermediate such as a paint, an adhesive, a pharmaceutical, cosmetics, food additive and surfactant It relates to a method of producing a compound.
　ジオキサン構造を有するアルコール化合物は、塗料や接着剤等の原料である環状アクリル酸エステルの中間体等として知られる。特許文献１には、ベンズアルデヒドとトリメチロールプロパンとの反応により得られる環状アルコール化合物が、環状アクリル酸エステルの中間体として開示されている。 Alcohol compounds having a dioxane structure are known as intermediates of cyclic acrylic acid esters which are raw materials for paints, adhesives and the like. Patent Document 1 discloses a cyclic alcohol compound obtained by the reaction of benzaldehyde and trimethylolpropane as an intermediate of a cyclic acrylic acid ester.
特開昭６０－７２８８４号公報Japanese Patent Application Laid-Open No. 60-72884
　特許文献１に記載されているベンズアルデヒドとトリメチロールプロパンとの反応により得られる環状アルコール化合物は、溶解性、反応性、耐熱性等の点で用途が限られることがある。
　本発明の課題は、塗料、接着剤、医薬品、化粧品、食品添加物及び界面活性剤等の原料及び中間体として有用な環状アルコール化合物、並びに当該化合物を製造する方法を提供することにある。 The cyclic alcohol compound obtained by the reaction of benzaldehyde and trimethylolpropane described in Patent Document 1 may have limited applications in terms of solubility, reactivity, heat resistance, and the like.
An object of the present invention is to provide cyclic alcohol compounds useful as raw materials and intermediates for paints, adhesives, pharmaceuticals, cosmetics, food additives and surfactants, and to provide methods for producing the compounds.
　本発明は、下記一般式（１）で表されるアルコール化合物を提供する。
Figure JPOXMLDOC01-appb-C000007
 （式中、Ａは、ベンゼン、ナフタレン、アントラセン、フェナントレン及びピレンからなる群から選ばれる芳香環を表す。Ｒ1は、炭素数１～１２のアルキル基、置換もしくは無置換の炭素数６～１０のアリール基又はハロゲン原子を表し、ｎは０～４の整数を表す。ただし、Ａがベンゼンの場合にはｎは１～４の整数を表す。ｎが２～４の整数を表す場合、複数のＲ1は、互いに同一でも異なっていてもよい。Ｒ2は水素原子、メチル基又はエチル基を表す。） The present invention provides an alcohol compound represented by the following general formula (1).
Figure JPOXMLDOC01-appb-C000007
 Wherein A represents an aromatic ring selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene and pyrene R 1 is an alkyl group having 1 to 12 carbon atoms, substituted or unsubstituted 6 to 10 carbon atoms And n represents an integer of 0 to 4, provided that when A is benzene, n represents an integer of 1 to 4. When n represents an integer of 2 to 4, plural R 1 s may be the same as or different from each other R 2 represents a hydrogen atom, a methyl group or an ethyl group)
　本発明のアルコール化合物は、塗料、接着剤、医薬品、化粧品、食品添加物及び界面活性剤等の原料及び中間体として好適に利用できる。特に、本発明のアルコール化合物を原料又は中間体として利用することで、バラエティに富んだ医薬品、化粧品、食品添加物及び界面活性剤等を製造することができる。 The alcohol compounds of the present invention can be suitably used as raw materials and intermediates for paints, adhesives, pharmaceuticals, cosmetics, food additives, surfactants and the like. In particular, various kinds of pharmaceuticals, cosmetics, food additives, surfactants and the like can be produced by using the alcohol compound of the present invention as a raw material or an intermediate.
　本発明のアルコール化合物は、下記一般式（１）で表される化合物である。
Figure JPOXMLDOC01-appb-C000008
 The alcohol compound of the present invention is a compound represented by the following general formula (1).
Figure JPOXMLDOC01-appb-C000008
　前記一般式（１）中、Ａは、ベンゼン、ナフタレン、アントラセン、フェナントレン及びピレンからなる群から選ばれる芳香環を表す。
　前記一般式（１）中、Ｒ1は、炭素数１～１２のアルキル基、置換もしくは無置換の炭素数６～１０のアリール基、又はハロゲン原子を表す。
　本発明におけるアルキル基は、炭素数１～１２、好ましくは炭素数１～９、より好ましくは炭素数１～４の直鎖、分岐又は環状アルキル基であり、具体例としてはメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ－ブチル基、シクロヘキシル基、プロピルシクロヘキシル基等が挙げられる。本発明におけるアリール基は、置換もしくは無置換の炭素数６～１０、好ましくは６～８のアリール基であり、具体例としてはフェニル基、ヨードフェニル基、ヒドロキシルフェニル基、ジヒドロキシフェニル基、メトキシヒドロキシフェニル基、エトキシヒドロキシフェニル基等が挙げられる。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。Ｒ1としては、原料の入手性の観点から、特にイソプロピル基、又はフェニル基が好ましい。
　前記一般式（１）中、ｎは０～４の整数を表す。ただし、Ａがベンゼンの場合にはｎは１～４の整数を表す。ｎが２～４の整数を表す場合、複数のＲ1は、互いに同一でも異なっていてもよいが同一であることがより好ましい。ｎは、原料の入手性の観点から、０又は１であることが好ましい。
　前記一般式（１）中、Ｒ2は水素原子、メチル基又はエチル基を表す。 In the general formula (1), A represents an aromatic ring selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene and pyrene.
In the general formula (1), R 1 represents an alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a halogen atom.
The alkyl group in the present invention is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, preferably 1 to 9 carbon atoms, more preferably 1 to 4 carbon atoms, and specific examples thereof include a methyl group and an ethyl group. And propyl, isopropyl, butyl, isobutyl, t-butyl, cyclohexyl, propylcyclohexyl and the like. The aryl group in the present invention is a substituted or unsubstituted aryl group having 6 to 10, preferably 6 to 8 carbon atoms, and specific examples thereof include a phenyl group, an iodophenyl group, a hydroxylphenyl group, a dihydroxyphenyl group, and methoxyhydroxy A phenyl group, ethoxy hydroxyphenyl group etc. are mentioned. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned. From the viewpoint of the availability of raw materials, R 1 is particularly preferably an isopropyl group or a phenyl group.
In the general formula (1), n represents an integer of 0 to 4. However, n is an integer of 1 to 4 when A is benzene. When n represents an integer of 2 to 4, the plurality of R 1 s may be the same as or different from each other, but are more preferably the same. n is preferably 0 or 1 from the viewpoint of the availability of the raw material.
In the general formula (1), R 2 represents a hydrogen atom, a methyl group or an ethyl group.
　前記一般式（１）で表されるアルコール化合物は、下記一般式（２）～（４）のいずれかで表されるアルコール化合物が好ましい。下記一般式（２）～（４）中、Ｒ2は、前記一般式（１）におけるＲ2と同義であり、好ましい範囲も同様である。
Figure JPOXMLDOC01-appb-C000009
 The alcohol compound represented by the general formula (1) is preferably an alcohol compound represented by any one of the following general formulas (2) to (4). In the following general formulas (2) to (4), R 2 has the same meaning as R 2 in the general formula (1), and the preferred range is also the same.
Figure JPOXMLDOC01-appb-C000009
　前記一般式（１）で表されるアルコール化合物の好ましい具体例としては、２－（ビフェニル－４－イル）－５－エチル－５－ヒドロキシメチル－１，３－ジオキサン、２－（ビフェニル－４－イル）－５－メチル－５－ヒドロキシメチル－１，３－ジオキサン、２－（ビフェニル－４－イル）－５－ヒドロキシメチル－１，３－ジオキサン、２－（イソプロピルフェニル－４－イル）－５－エチル－５－ヒドロキシメチル－１，３－ジオキサン、２－（１－ナフチル）－５－エチル－５－ヒドロキシメチル－１，３－ジオキサン等が挙げられるが、本発明はこれらに限定されない。 Preferred specific examples of the alcohol compound represented by the above general formula (1) include 2- (biphenyl-4-yl) -5-ethyl-5-hydroxymethyl-1,3-dioxane, 2- (biphenyl-4) -Yl) -5-methyl-5-hydroxymethyl-1,3-dioxane, 2- (biphenyl-4-yl) -5-hydroxymethyl-1,3-dioxane, 2- (isopropylphenyl-4-yl) -5-ethyl-5-hydroxymethyl-1,3-dioxane, 2- (1-naphthyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane etc., but the present invention is not limited thereto. I will not.
　前記一般式（１）で表されるアルコール化合物の製造方法は特に限定されないが、下記一般式（Ａ）で表される芳香族アルデヒド１モルに対し、トリメチロールメタン、トリメチロールエタン又はトリメチロールプロパン等の３価アルコールを１～５モル、好ましくは１～２モル、より好ましくは１～１．２モルを反応させることにより製造する方法が好ましい。３価アルコールを上記範囲で使用することにより、副生成物の生成を著しく軽減でき、生産効率が向上する。 Although the manufacturing method of the alcohol compound represented by said General formula (1) is not specifically limited, To 1 mol of aromatic aldehydes represented by the following general formula (A), trimethylol methane, trimethylol ethane, or trimethylol propane is mentioned. And the like are preferably produced by reacting 1 to 5 moles, preferably 1 to 2 moles, more preferably 1 to 1.2 moles of a trihydric alcohol such as By using a trihydric alcohol in the above range, the formation of by-products can be significantly reduced and the production efficiency is improved.
Figure JPOXMLDOC01-appb-C000010
 （式中、Ａ、Ｒ1及びｎは、前記一般式（１）におけるＡ、Ｒ1及びｎと同義である。）
Figure JPOXMLDOC01-appb-C000010
 (Wherein, A, R 1 and n, the A in the general formula (1) have the same meanings as R 1 and n.)
　本発明のアルコール化合物の製造方法において、反応温度は、好ましくは２０～２００℃、より好ましくは１００～１８０℃、特に好ましくは１２０～１６０℃である。上記範囲温度で製造することにより目的化合物が効率よく製造できる。 In the method for producing an alcohol compound of the present invention, the reaction temperature is preferably 20 to 200 ° C., more preferably 100 to 180 ° C., particularly preferably 120 to 160 ° C. By producing at the above temperature range, the target compound can be efficiently produced.
　本発明のアルコール化合物の製造方法では、３価アルコールの有機溶剤溶液に酸触媒下で前記芳香族アルデヒドを滴下して反応させることが好ましい。このことにより副生成物の生成を著しく低減でき、生産効率を向上させることができる。また、反応中は、ディーンシュターク管等により溶媒中の水を留去することが好ましい。 In the method for producing an alcohol compound of the present invention, it is preferable that the above-mentioned aromatic aldehyde be dropped in an organic solvent solution of a trihydric alcohol under acid catalyst to be reacted. This can significantly reduce the formation of by-products and can improve the production efficiency. During the reaction, it is preferable to distill off water in the solvent by means of a Dean-Stark tube or the like.
　本発明に使用できる触媒としては、塩酸、硫酸、リン酸、パラトルエンスルホン酸、メタンスルホン酸等の酸触媒を使用することが好ましく、パラトルエンスルホン酸が特に好ましい。また、使用する酸触媒量は芳香族アルデヒドに対して０．１～３０質量％が好ましく、特に好ましくは１～２０質量％である。 As a catalyst that can be used in the present invention, it is preferable to use an acid catalyst such as hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid and the like, and p-toluenesulfonic acid is particularly preferable. The amount of acid catalyst used is preferably 0.1 to 30% by mass, particularly preferably 1 to 20% by mass, with respect to the aromatic aldehyde.
　本発明に使用される反応溶媒は限定されないが、ベンゼン、トルエン、キシレン、メシチレン、アニソール等の芳香族炭化水素系溶剤；ジメチルホルムアミド、ジメチルアセトアミド等のアミド系溶剤；テトラヒドロフラン、ジオキサン、ジオキソラン等のエーテル系溶剤；酢酸エチル、酢酸ブチル等のエステル系溶媒等が挙げられる。特にトルエン、ジメチルホルムアミド、ジメチルアセトアミドが好ましい。 The reaction solvent used in the present invention is not limited, but aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, anisole; amide solvents such as dimethylformamide, dimethylacetamide; ethers such as tetrahydrofuran, dioxane, dioxolane And ester solvents such as ethyl acetate and butyl acetate. In particular, toluene, dimethylformamide and dimethylacetamide are preferred.
　以下、本発明を実施例に基づいて詳細に説明するが、本発明はこれに限定されるものではない。 Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited thereto.
実施例１
［２－（ビフェニル－４－イル）－５－エチル－５－ヒドロキシメチル－１，３－ジオキサンの合成］
Figure JPOXMLDOC01-appb-C000011
 　５０００ｍｌフラスコ内にジメチルアセトアミド（以下ＤＭＡｃと称する、和光純薬工業（株）製、特級）２０００ｍｌ、トルエン（和光純薬工業（株）製、特級）７００ｍｌ、トリメチロールプロパン（和光純薬工業（株）製、特級）８８．８ｇ（０．７４ｍｏｌ）、パラトルエンスルホン酸二水和物（和光純薬工業（株）製、特級）２０ｇを投入し、１００℃で撹拌した。その後、４－ビフェニルアルデヒド（和光純薬工業（株）製、特級）１３４ｇ（０．７４ｍｏｌ）のトルエン７００ｍｌ溶液を滴下し、１４５℃まで昇温した。水を含有する留出液を分離し、反応時間５時間で反応を終了した。反応液に水５Ｌ投入したところ白色結晶が析出した。濾過水洗後、濃縮することにより白色結晶（収率：９８％）を得た。
　得られた生成物について1Ｈ－ＮＭＲスペクトルを測定した。測定には、ＮＭＲ装置（Ｈｉｔａｃｈｉ社製、商品名：Ｒ－９０Ｈ）を用い、内部標準物質としてテトラメチルシラン（以下、ＴＭＳと称する。）を用いた。得られた生成物の重ジメチルスルホキシド（以下、重ＤＭＳＯと称する、和光純薬工業（株）製、特級）溶媒中での1Ｈ－ＮＭＲのケミカルシフト値（δｐｐｍ，ＴＭＳ基準）は、０．８－０．９（ｔ，３Ｈ）、１．６－１．７（ｑ，２Ｈ）、３．４（ｓ，２Ｈ）、３．６－３．８（ｄｄ，４Ｈ）、４．７（ｓ，１Ｈ）、５．５（ｓ，１Ｈ）、７．３－７．８（ｍ，９Ｈ）であった。 Example 1
[Synthesis of 2- (biphenyl-4-yl) -5-ethyl-5-hydroxymethyl-1,3-dioxane]
Figure JPOXMLDOC01-appb-C000011
 2000 ml of dimethyl acetamide (hereinafter referred to as DMAc, special grade: Wako Pure Chemical Industries, Ltd., special grade), 700 ml of toluene (special grade, Wako Pure Chemical Industries, Ltd.), trimethylolpropane (Wako Pure Chemical Industries, Ltd. 8 g (0.74 mol) made of special grade) and 20 g of p-toluenesulfonic acid dihydrate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) were added and stirred at 100 ° C. Thereafter, a solution of 134 g (0.74 mol) of 4-biphenyl aldehyde (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) in 700 ml of toluene was dropped, and the temperature was raised to 145.degree. The distillate containing water was separated, and the reaction was completed in 5 hours of reaction time. When 5 liters of water was added to the reaction solution, white crystals were precipitated. After filtration and washing with water, concentration gave white crystals (yield: 98%).
The 1 H-NMR spectrum was measured for the obtained product. For measurement, an NMR apparatus (manufactured by Hitachi, trade name: R-90H) was used, and tetramethylsilane (hereinafter referred to as TMS) was used as an internal standard substance. The chemical shift value of 1 H-NMR in a solvent of heavy dimethyl sulfoxide (hereinafter referred to as heavy DMSO, manufactured by Wako Pure Chemical Industries, Ltd., special grade) of the obtained product is 0.1. 8-0.9 (t, 3 H), 1.6-1.7 (q, 2 H), 3.4 (s, 2 H), 3.6-3.8 (dd, 4 H), 4.7 ( s, 1 H), 5.5 (s, 1 H), 7.3-7.8 (m, 9 H).
実施例２
［２－（ビフェニル－４－イル）－５－メチル－５－ヒドロキシメチル－１，３－ジオキサンの合成］
Figure JPOXMLDOC01-appb-C000012
 　トリメチロールプロパンをトリメチロールエタンに変更したこと以外は実施例１と同様にして合成及び分析を行った。収率は９１％であった。得られた生成物の重ＤＭＳＯ溶媒中での1Ｈ－ＮＭＲのケミカルシフト値（δｐｐｍ，ＴＭＳ基準）は、１．０（ｓ，３Ｈ）、３．４－３．９（ｍ，６Ｈ）、４．７（ｓ，１Ｈ）、５．９（ｓ，１Ｈ）、７．４－７．５（ｍ，９Ｈ）であった。 Example 2
Synthesis of 2- (biphenyl-4-yl) -5-methyl-5-hydroxymethyl-1,3-dioxane
Figure JPOXMLDOC01-appb-C000012
 The synthesis and analysis were carried out in the same manner as in Example 1 except that trimethylolpropane was changed to trimethylolethane. The yield was 91%. The chemical shifts of 1 H-NMR in a heavy DMSO solvent of the product obtained (δ ppm, relative to TMS) are 1.0 (s, 3 H), 3.4-3.9 (m, 6 H), It was 4.7 (s, 1 H), 5.9 (s, 1 H), 7.4-7.5 (m, 9 H).
実施例３
［２－（ビフェニル－４－イル）－５－ヒドロキシメチル－１，３－ジオキサンの合成］
Figure JPOXMLDOC01-appb-C000013
 　トリメチロールプロパンをトリメチロールメタンに変更したこと以外は実施例１と同様にして合成及び分析を行った。収率は８９％であった。得られた生成物の重ＤＭＳＯ溶媒中での1Ｈ－ＮＭＲのケミカルシフト値（δｐｐｍ，ＴＭＳ基準）は、１．８（ｓ，１Ｈ）、３．４－３．９（ｍ，６Ｈ）、４．７（ｓ，１Ｈ）、５．９（ｓ，１Ｈ）、７．４－７．５（ｍ，９Ｈ）であった。 Example 3
[Synthesis of 2- (biphenyl-4-yl) -5-hydroxymethyl-1,3-dioxane]
Figure JPOXMLDOC01-appb-C000013
 The synthesis and analysis were carried out in the same manner as in Example 1 except that trimethylolpropane was changed to trimethylolmethane. The yield was 89%. The chemical shifts of 1 H-NMR in a heavy DMSO solvent of the product obtained (δ ppm, relative to TMS) are 1.8 (s, 1 H), 3.4-3.9 (m, 6 H), It was 4.7 (s, 1 H), 5.9 (s, 1 H), 7.4-7.5 (m, 9 H).
実施例４
［２－（イソプロピルフェニル－４－イル）－５－エチル－５－ヒドロキシメチル－１，３－ジオキサンの合成］
Figure JPOXMLDOC01-appb-C000014
 　４－ビフェニルアルデヒドをクミンアルデヒドに変更したこと以外は実施例１と同様にして合成及び分析を行った。収率は９２％であった。得られた生成物の重ＤＭＳＯ溶媒中での1Ｈ－ＮＭＲのケミカルシフト値（δｐｐｍ，ＴＭＳ基準）は、０．９（ｔ，３Ｈ）、１．２（ｄ，６Ｈ）、１．７（ｑ，２Ｈ）、２．９（ｍ，１Ｈ）、３．４－３．９（ｍ，６Ｈ）、４．７（ｓ，１Ｈ）、５．９（ｓ，１Ｈ）、７．２－７．４（ｄｄ，４Ｈ）であった。 Example 4
Synthesis of 2- (isopropylphenyl-4-yl) -5-ethyl-5-hydroxymethyl-1,3-dioxane
Figure JPOXMLDOC01-appb-C000014
 The synthesis and analysis were carried out in the same manner as in Example 1 except that 4-biphenylaldehyde was changed to cuminaldehyde. The yield was 92%. The chemical shifts of 1 H-NMR in a heavy DMSO solvent of the obtained product (δ ppm, based on TMS) are 0.9 (t, 3 H), 1.2 (d, 6 H), 1.7 (1.7 ppm). q, 2H), 2.9 (m, 1 H), 3.4-3.9 (m, 6 H), 4.7 (s, 1 H), 5.9 (s, 1 H), 7.2-7 .4 (dd, 4H).
実施例５
［２－（１－ナフチル）－５－エチル－５－ヒドロキシメチル－１，３－ジオキサンの合成］
Figure JPOXMLDOC01-appb-C000015
 　ビフェニルアルデヒドをナフチルアルデヒドに変更したこと以外は実施例１と同様にして合成及び分析を行った。収率は８７％であった。得られた生成物の重ＤＭＳＯ溶媒中での1Ｈ－ＮＭＲのケミカルシフト値（δｐｐｍ，ＴＭＳ基準）は、０．８－０．９（ｔ，３Ｈ）、１．６－１．７（ｑ，２Ｈ）、３．４－３．８（ｍ，６Ｈ）、４．７（ｑ，１Ｈ）、５．５（ｓ，１Ｈ）、７．０－８．２（ｍ，７Ｈ）であった。 Example 5
Synthesis of 2- (1-Naphthyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane
Figure JPOXMLDOC01-appb-C000015
 The synthesis and analysis were carried out in the same manner as in Example 1 except that biphenylaldehyde was changed to naphthylaldehyde. The yield was 87%. The chemical shifts of 1 H-NMR in a heavy DMSO solvent of the obtained product (δ ppm, based on TMS) are 0.8-0.9 (t, 3 H), 1.6-1.7 (q) , 2H), 3.4-3.8 (m, 6H), 4.7 (q, 1H), 5.5 (s, 1H), and 7.0-8.2 (m, 7H). .
　本発明のアルコール化合物は、塗料、接着剤、医薬品、化粧品、食品添加物及び界面活性剤等の原料及び中間体として好適に利用でき、工業的価値が高い。特に、従来のアルコール化合物が原料又は中間体として利用できない場合であっても、本発明のアルコール化合物を原料又は中間体として利用することができ、種々の塗料、接着剤、医薬品、化粧品、食品添加物及び界面活性剤等を製造することができ、技術を豊富化することができる。 The alcohol compounds of the present invention can be suitably used as raw materials and intermediates for paints, adhesives, pharmaceuticals, cosmetics, food additives, surfactants and the like, and have high industrial value. In particular, even when a conventional alcohol compound can not be used as a raw material or an intermediate, the alcohol compound of the present invention can be used as a raw material or an intermediate, and various paints, adhesives, pharmaceuticals, cosmetics, food additives are added. Substances and surfactants can be produced, and the technology can be enriched.

Claims (5)

  1. 　下記一般式（１）で表されるアルコール化合物。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ａは、ベンゼン、ナフタレン、アントラセン、フェナントレン及びピレンからなる群から選ばれる芳香環を表す。Ｒ1は、炭素数１～１２のアルキル基、置換もしくは無置換の炭素数６～１０のアリール基又はハロゲン原子を表し、ｎは０～４の整数を表す。ただし、Ａがベンゼンの場合にはｎは１～４の整数を表す。ｎが２～４の整数を表す場合、複数のＲ1は、互いに同一でも異なっていてもよい。Ｒ2は水素原子、メチル基又はエチル基を表す。）     The alcohol compound represented by following General formula (1).
    Figure JPOXMLDOC01-appb-C000001
     Wherein A represents an aromatic ring selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene and pyrene R 1 is an alkyl group having 1 to 12 carbon atoms, substituted or unsubstituted 6 to 10 carbon atoms And n represents an integer of 0 to 4, provided that when A is benzene, n represents an integer of 1 to 4. When n represents an integer of 2 to 4, plural R 1 s may be the same as or different from each other R 2 represents a hydrogen atom, a methyl group or an ethyl group)
  2. 　下記一般式（２）で表される請求項１に記載のアルコール化合物。
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ2は水素原子、メチル基又はエチル基を表す。）     The alcohol compound of Claim 1 represented by following General formula (2).
    Figure JPOXMLDOC01-appb-C000002
     (Wherein, R 2 represents a hydrogen atom, a methyl group or an ethyl group)
  3. 　下記一般式（３）で表される請求項１に記載のアルコール化合物。
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｒ2は水素原子、メチル基又はエチル基を表す。）     The alcohol compound of Claim 1 represented by following General formula (3).
    Figure JPOXMLDOC01-appb-C000003
     (Wherein, R 2 represents a hydrogen atom, a methyl group or an ethyl group)
  4. 　下記一般式（４）で表される請求項１に記載のアルコール化合物。
    Figure JPOXMLDOC01-appb-C000004
     （式中、Ｒ2は水素原子、メチル基又はエチル基を表す。）     The alcohol compound of Claim 1 represented by following General formula (4).
    Figure JPOXMLDOC01-appb-C000004
     (Wherein, R 2 represents a hydrogen atom, a methyl group or an ethyl group)
  5. 　下記一般式（Ａ）で表される芳香族アルデヒド１モルに対し、トリメチロールメタン、トリメチロールエタン及びトリメチロールプロパンからなる群から選ばれる３価アルコールを１～５モルを反応させる、下記一般式（１）で表されるアルコール化合物の製造方法。
    Figure JPOXMLDOC01-appb-C000005
     （式中、Ａは、ベンゼン、ナフタレン、アントラセン、フェナントレン及びピレンからなる群から選ばれる芳香環を表す。Ｒ1は、炭素数１～１２のアルキル基、置換もしくは無置換の炭素数６～１０のアリール基又はハロゲン原子を表し、ｎは０～４の整数を表す。ただし、Ａがベンゼンの場合にはｎは１～４の整数を表す。ｎが２～４の整数を表す場合、複数のＲ1は、互いに同一でも異なっていてもよい。Ｒ2は水素原子、メチル基又はエチル基を表す。）
    Figure JPOXMLDOC01-appb-C000006
     （式中、Ａ、Ｒ1及びｎは、前記一般式（１）におけるＡ、Ｒ1及びｎと同義である。）     1 to 5 moles of a trihydric alcohol selected from the group consisting of trimethylolmethane, trimethylolethane and trimethylolpropane are reacted with 1 mole of the aromatic aldehyde represented by the following formula (A): The manufacturing method of the alcohol compound represented by (1).
    Figure JPOXMLDOC01-appb-C000005
     Wherein A represents an aromatic ring selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene and pyrene R 1 is an alkyl group having 1 to 12 carbon atoms, substituted or unsubstituted 6 to 10 carbon atoms And n represents an integer of 0 to 4, provided that when A is benzene, n represents an integer of 1 to 4. When n represents an integer of 2 to 4, plural R 1 s may be the same as or different from each other R 2 represents a hydrogen atom, a methyl group or an ethyl group)
    Figure JPOXMLDOC01-appb-C000006
     (Wherein, A, R 1 and n, the A in the general formula (1) have the same meanings as R 1 and n.)
PCT/JP2010/051110 2009-01-30 2010-01-28 Alcohol compound having dioxane structure and process for producing same WO2010087394A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US13/146,752 US8324407B2 (en) 2009-01-30 2010-01-28 Alcohol compound having dioxane structure and process for producing same
JP2010548547A JPWO2010087394A1 (en) 2009-01-30 2010-01-28 Alcohol compound having dioxane structure and process for producing the same
CN201080006099.6A CN102300856A (en) 2009-01-30 2010-01-28 Alcohol compound having dioxane structure and process for producing same
EP10735859A EP2392569A4 (en) 2009-01-30 2010-01-28 Alcohol compound having dioxane structure and process for producing same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009019591 2009-01-30
JP2009-019591 2009-01-30

Publications (1)

Publication Number Publication Date
WO2010087394A1 true WO2010087394A1 (en) 2010-08-05

Family

ID=42395652

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/051110 WO2010087394A1 (en) 2009-01-30 2010-01-28 Alcohol compound having dioxane structure and process for producing same

Country Status (7)

Country Link
US (1) US8324407B2 (en)
EP (1) EP2392569A4 (en)
JP (1) JPWO2010087394A1 (en)
KR (1) KR20110107825A (en)
CN (1) CN102300856A (en)
TW (1) TW201031647A (en)
WO (1) WO2010087394A1 (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5083377A (en) * 1973-11-21 1975-07-05
JPS6072884A (en) 1983-09-30 1985-04-24 Toagosei Chem Ind Co Ltd Cyclic acrylic acid ester
JPH0219373A (en) * 1988-05-24 1990-01-23 Hoechst Celanese Corp Production of monohydroxy monocyclic acetal and ester thereof
JPH03122104A (en) * 1989-09-22 1991-05-24 Natl Starch & Chem Investment Holding Corp Monomer and polymer which contain acetal and aldehyde group
PL162441B1 (en) * 1990-01-03 1993-12-31 Politechnika Wroclawska Method for manufacturing new, surface-active sodium sulphate derivatives of 2,5-di and 2,2,5-tri substituted 5-hydroxymethyl-1,3-dioxanes
PL163371B1 (en) * 1990-08-14 1994-03-31 Politechnika Wroclawska Method of producing new chemodegradable block copolymer alkyloxiranes
JP2001031671A (en) * 1999-07-15 2001-02-06 Kao Corp Production of ether acetal
JP2001206882A (en) * 2000-01-26 2001-07-31 Kuraray Co Ltd Cyclic acetal derivative

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4808939A (en) 1988-04-04 1989-02-28 Unisys Corporation Variable rate rectangular matched filter
US5258477A (en) 1989-09-22 1993-11-02 National Starch And Chemical Investment Holding Corporation Monomers and polymers containing acetal and aldehyde groups
JP2004292470A (en) * 2003-03-25 2004-10-21 New Japan Chem Co Ltd Melt viscosity-reducing agent for polyester resin, polyester resin composition comprising the same, and fiber and molded product obtained from the resin composition
JP5083377B2 (en) 2010-06-11 2012-11-28 株式会社日本自動車部品総合研究所 Valve timing adjustment device

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5083377A (en) * 1973-11-21 1975-07-05
JPS6072884A (en) 1983-09-30 1985-04-24 Toagosei Chem Ind Co Ltd Cyclic acrylic acid ester
JPH0219373A (en) * 1988-05-24 1990-01-23 Hoechst Celanese Corp Production of monohydroxy monocyclic acetal and ester thereof
JPH03122104A (en) * 1989-09-22 1991-05-24 Natl Starch & Chem Investment Holding Corp Monomer and polymer which contain acetal and aldehyde group
PL162441B1 (en) * 1990-01-03 1993-12-31 Politechnika Wroclawska Method for manufacturing new, surface-active sodium sulphate derivatives of 2,5-di and 2,2,5-tri substituted 5-hydroxymethyl-1,3-dioxanes
PL163371B1 (en) * 1990-08-14 1994-03-31 Politechnika Wroclawska Method of producing new chemodegradable block copolymer alkyloxiranes
JP2001031671A (en) * 1999-07-15 2001-02-06 Kao Corp Production of ether acetal
JP2001206882A (en) * 2000-01-26 2001-07-31 Kuraray Co Ltd Cyclic acetal derivative

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HANNIG, EGON ET AL.: "Preparation of some 2- substituted 5-ethyl-5-hydroxymethyl-1,3- dioxanes and their carbamic acid esters", PHARMAZIE, vol. 24, no. 1, 1969, pages 32 - 35, XP009140727 *
See also references of EP2392569A4 *
SHOSTAKOVSKII, M. F. ET AL.: "Chemistry of trimethylolethane. II. Vinylation of trimethylolethane and some 2,5-dialkyl(alkyl, aryl)-5-methylol-1,3-dioxanes", IZVESTIYA AKADEMII NAUK SSSR, SERIYA KHIMICHESKAYA, 1966, pages 133 - 137, XP008166641 *

Also Published As

Publication number Publication date
KR20110107825A (en) 2011-10-04
EP2392569A1 (en) 2011-12-07
EP2392569A4 (en) 2012-08-01
US20110282076A1 (en) 2011-11-17
JPWO2010087394A1 (en) 2012-08-02
TW201031647A (en) 2010-09-01
CN102300856A (en) 2011-12-28
US8324407B2 (en) 2012-12-04

Similar Documents

Publication Publication Date Title
KR20150113005A (en) Novel aryl compound and method for producing same
JPWO2018074305A1 (en) Diol, process for producing diol, di (meth) acrylate and process for producing di (meth) acrylate
JP2008024650A (en) Optically active macrocyclic compound, method for producing the same and use thereof
WO2011035532A1 (en) Preparation method of aromatic borate ester compound
WO2021010363A1 (en) Method for producing binaphthyls
JP2006160663A (en) Method for producing 1,1'-bis(2-hydroxynaphthyl)
JP2005330283A (en) Method for producing phthaloyl chloride
JP2012207008A (en) Crystalline polymorph of 6,6-(9-fluorenylidene)-di(2-naphthol) and method for producing the same
WO2010087394A1 (en) Alcohol compound having dioxane structure and process for producing same
JP6247992B2 (en) Method for producing halogen compound
US20040171863A1 (en) Process for poducing beta-oxonitrile compound or alkali metal salt thereof
JP6635999B2 (en) Method for producing potassium salt, and potassium salt
JP6466107B2 (en) 4-Phenylthio-5- (trifluoromethyl) pyrimidine derivative and method for producing the same
EP2155653B1 (en) Process for preparing alkyl alkoxybenzoates in one step
JP2004262863A (en) Method for producing orthobenzidine compound
WO2011158813A1 (en) Method for producing n-substituted-2-amino-4-(hydroxymethylphosphinyl)-2-butenoic acid
KR20080094075A (en) Process for preparing 3,4-disubstituted phenylacetic acids and novel intermediates
JP5783371B2 (en) 10-substituted-1,4-dihydro-1,4-methanoanthracen-9-yl- (meth) acrylate compound and method for producing the same
JP2008297228A (en) Method for producing hydroquinone derivative
JP2010184904A (en) Method for producing acetic acid compound
JPH0940596A (en) Production of 2,3,6,7,10,11-hexaalkoxytriphenylenes
JP2007131600A (en) Production method for fluorine-containing lactic acid derivative, and its intermediate
JP2008201730A (en) Method for producing aromatic compound
JP2006008522A (en) Method for producing 2,3-dihydroxy-4-alkoxy-acylbenzenes
JP2006282542A (en) Manufacturing method of croconic acid or salt thereof

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080006099.6

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10735859

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2010548547

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 13146752

Country of ref document: US

Ref document number: 2010735859

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 20117017857

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE